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    • 专利摘要:
    The fuel composition comprises a major amount of fuel and an effective minor amount of a quaternary ammonium salt exhibiting a thermogravimetric analysis (TGA) weight loss of greater than 50% by weight at 350 ° C. The quantity of quaternary ammonium salt present in the fuel is sufficient to improve the efficiency of the diesel engine with direct fuel injection.
    公开号:BE1021421B1
    申请号:E2012/0741
    申请日:2012-10-31
    公开日:2015-11-19
    发明作者:Xinggao Fang；Julienne M. Galante-Fox
    申请人:Afton Chemical Corporation；
    IPC主号:
    专利说明:

    The present invention relates to fuel additives and additives and concentrated additives which include additives which are used to improve engine performance. [0001] The present invention relates to fuel additives and additives and concentrated additives which include additives which are used to improve engine performance. with direct fuel injection. In particular, the application relates to a fuel additive that is effective in improving the efficiency of direct fuel injectors for diesel engines. BACKGROUND AND SUMMARY [0002] It has long been desired to maximize the fuel economy, horsepower and driveability of diesel powered vehicles while improving acceleration, reducing emissions and preventing hesitation. While it is known to improve the performance of gasoline engines by using dispersants to keep valves and fuel injectors clean in fuel injection engines in the intake, these dispersants are not necessarily effective in diesel engines with direct fuel injection. The reasons for this unpredictability lie in the differences between direct and indirect fuel injection engines and fuels for these engines.
    [0003] For example, there is a very big difference between diesel engines with indirect fuel injection and more modern diesel engines with direct fuel injection by high pressure common rail (RCHP). Similarly, low sulfur diesel fuels and ultra low sulfur diesel fuels are now commonly available on the market for such engines. "Low sulfur" diesel fuel means a fuel having a sulfur content of 50 ppm by weight, or less, based on the total weight of the fuel. A "very low sulfur" diesel fuel (DTFS) means a fuel having a sulfur content of 15 ppm by weight, or less, based on the total weight of the fuel. Injectors in an RCHP engine operate at much higher pressures and temperatures than older models of engines and injection systems. The combination of low sulfur fuels or DTFS and RCHP engines has led to a change in the type of injector deposits and in the frequency of formation of injectors deposits currently found on the market.
    [0004] Over the years, dispersant compositions have been developed for diesel fuels. Dispersant compositions known in the art for use in fuels include compositions that may contain polyalkylene succinimides, polyamines, and polyalkyl-substituted Mannich compounds. Dispersants are able to retain soot and slurry in a fluid, however the dispersants are not particularly effective at cleaning surfaces once deposits have formed on the surfaces.
    [0005] Therefore, fuel compositions for direct injection diesel engines often produce undesirable deposits in the engines. Therefore, improved compositions that can prevent build up of deposits, maintaining "original" cleanliness for the life of the vehicle are desirable. Ideally, the same composition that can clean the fouled fuel injectors while restoring their performance to the "original" condition would be both desirable and useful in reducing exhaust emissions in the environment. air and to improve the power output of the engines.
    [0006] In accordance with the present invention, exemplary embodiments provide a diesel fuel composition for an internal combustion engine comprising a method for improving the performance of fuel injectors and a method for cleaning fuel injectors for fuel injection. an internal combustion engine. The fuel composition comprises a major amount of diesel fuel and a minor effective amount of quaternary ammonium salt having thermogravimetric (TGA) weight loss of greater than 50 wt% at 350 ° C. The amount of quaternary ammonium salt present in the fuel is sufficient to improve the performance of a diesel engine with direct fuel injection having consumed the composition compared to the performance of such a motor having consumed a fuel composition which does not does not contain quaternary ammonium salt.
    Another embodiment of the present invention provides a method of improving the performance of the injectors of a diesel engine with direct fuel injection. The method comprises operating the engine with a fuel composition that contains a major amount of fuel and from about 5 to about 200 ppm by weight, based on the total fuel weight, of a quaternary ammonium salt having a weight loss by thermogravimetric analysis (TGA) greater than 50% by weight at 350 ° C. The quaternary ammonium salt present in the fuel improves the performance of the engine injectors by at least about 80% when measured according to the CEC F-98-08 protocol for direct injection.
    Another embodiment of the present invention discloses a method of operating a diesel engine with direct fuel injection. The method comprises combustion in the engine of a fuel composition containing a major amount of fuel and from about 5 to about 200 ppm by weight, based on the total fuel weight, of a quaternary ammonium salt having a weight loss by thermogravimetric analysis (ATG) greater than 50% by weight at 350 ° C. In other embodiments, the weight loss by ATG is greater than 70% by weight, for example greater than 80% by weight, and in particular greater than 90% by weight.
    Another embodiment of the present invention provides a concentrated additive for a fuel for use in a direct injection diesel engine. The concentrated additive comprises a quaternary ammonium salt having a thermogravimetric weight loss (TGA) greater than 50% by weight at 350 ° C and at least one component selected from the group consisting of diluents, compatibilizers, corrosion inhibitors, cold flow improvers (CFPP additives), freezing point depressants, solvents, demulsifiers, lubricating additives, modifiers friction agents, amine stabilizers, combustion improvers, dispersants, antioxidants, heat stabilizers, conductivity enhancers, metal deactivators, marking dyes, organic nitrate ignition accelerators, and cyclomatic tricarbonyl manganese compounds.
    An advantage of the fuel additive described herein is that the additive can not only reduce the amount of deposits forming on direct fuel injectors, but also be effective in cleaning the fouled injectors sufficiently to provide recovery of fuel. increased power for the engine.
    Additional embodiments and advantages of the present invention will be partially demonstrated in the following detailed description, and / or may be observed by the practice of the present invention. It is to be understood that the foregoing general description and the following detailed description are given solely by way of example and explanation and have no restrictive effect on the present invention as claimed.
    DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
    The fuel additive component of the present invention may be used in a minor amount in a major amount of fuel and may be added to the fuel directly or added as a component of a fuel additive. A fuel additive component particularly suitable for improving the operation of internal combustion engines can be produced by a wide variety of well known reaction techniques with amines or polyamines. For example, such an additive component can be produced by reacting a tertiary amine of the formula
    wherein each of R1, R2 and R3 is selected from hydrocarbyl groups containing from 1 to 50 carbon atoms, with a quaternizing agent to provide a component of the formula:
    wherein each of R1, R2, R3 and R4 is selected from hydrocarbyl groups containing from 1 to 50 carbon atoms, wherein at least one and not more than three of R1, R2, R3 and R4 is a hydrocarbyl group containing 1 to 4 carbon atoms and at least one of R1, R2, R3 and R4 is a hydrocarbyl group containing from 8 to 50 carbon atoms, M 'is selected from the group consisting of a carboxylate, a nitrate, a nitride, a nitrite, a hyponitrite, a phenate, a carbamate, a carbonate, a halide, a sulphate, a sulphite, a sulphide, a sulfonate, a phosphate, a phosphonate, and the like. In one embodiment, R1, R2, R3 and R4 are each selected from hydrocarbyl groups containing from 1 to 20 carbon atoms, provided that at least one of R1, R2, R3 and R4 contains from 8 to 20 carbon atoms. carbon. In another embodiment, each of R1, R2, R3 and R4 is selected from an alkyl or alkenyl group.
    Suitable quaternizing agents may be selected from the group consisting of carboxylates, carbonates, cyclic carbonates, phenates, hydrocarbyl substituted epoxides, or mixtures thereof. In one embodiment, the quaternization agent may be derived from a hydrocarbyl (or alkyl) substituted carbonate. In another embodiment, the quaternizing agent may be selected from a hydrocarbyl substituted epoxide. In another embodiment, the quaternization agent may be selected from a hydrocarbyl substituted carboxylate. In one embodiment, the carboxylate quaternarizer excludes oxalates.
    As used herein, the term "hydrocarbyl group" or "hydrocarbyl" is used in its ordinary meaning, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of a molecule and having a predominantly hydrocarbon character. Examples of hydrocarbyl groups include: (1) hydrocarbon substituents, namely, aliphatic (e.g. alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic and alicyclic substituted aromatic substituents, as well as cyclic substituents in which the ring is supplemented by another part of the molecule (for example, two substituents together form an alicyclic radical); (2) substituted hydrocarbon substituents, that is to say substituents containing non-hydrocarbon groups which, in the context of the present description, do not modify the predominantly hydrocarbon substituent (for example, halo (in particular chloro and fluoro), hydroxy alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino and sulfoxy); (3) hetero-substituents, namely substituents which, while having a predominantly hydrocarbon character, in the context of this specification, contain elements other than carbon in a ring or chain otherwise composed of carbon atoms; carbon. Hetero atoms include sulfur, oxygen, and nitrogen, and include substituents such as pyridyl, furyl, thienyl, and imidazolyl. In general, not more than two, or as a further example, no more than one non-hydrocarbon substituent is present per ten carbon atoms in the hydrocarbyl group; in some embodiments, no non-hydrocarbon substituent is present in the hydrocarbyl group.
    As used herein, the term "major amount" is understood to mean an amount greater than or equal to 50% by weight, for example from about 80 to about 98% by weight based on the total weight of the composition. Furthermore, as used herein, the term "minor amount" is understood to mean less than 50% by weight based on the total weight of the composition.
    Methods for producing quaternary ammonium salts include, but are not limited to, ion exchange reactions, or the direct alkylation of an amine or tertiary polyamine. Direct alkylation may include methylation of tertiary amines such as pyridine and isoquinoline with methyl carboxylates, or alkylation of a tertiary amine with a hydrocarbyl epoxide in a one or two step reaction.
    Amine Compound [0017] In one embodiment, a tertiary amine comprising monoamines and polyamines can be reacted with a quaternizing agent. Suitable tertiary amine compounds of the formula
    wherein each of R1, R2 and R3 is selected from hydrocarbyl groups containing from 1 to 50 carbon atoms. Each hydrocarbyl group R 1 to R 3 may independently be linear, branched, substituted, cyclic, saturated, unsaturated, or contain one or more hetero atoms. Suitable hydrocarbyl groups may include, but are not limited to, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, alkoxy groups, aryloxy groups and the like. Particularly suitable hydrocarbyl groups may be linear or branched alkyl groups. Some representative examples of amino reactants that can be quaternized to produce compounds of the present invention are: trimethylamine, triethylamine, tri-n-propylamine, dimethyl ethylamine, dimethyl lauryl amine, dimethylolamine amine, dimethyl stearyl amine, dimethyl eicosyl amine, dimethyl octadecyl amine, N-methyl piperidine, Ν, Ν'-dimethyl piperazine, N-methyl-N'-ethyl piperazine, N-methyl morpholine, N-ethyl morpholine, N-hydroxyethyl morpholine, pyridine, triethanolamine, triisopropanolamine, methyl diethanolamine , dimethyl ethanolamine, lauryl diisopropanolamine, stearyl diethanolamine, dioleyl ethanolamine, dimethyl isobutanolamine, methyl diisooctanolamine, dimethyl propenylamine, dimethyl butenylamine, dimethyl octenylamine, ethyl didodecenylamine, dibutyl eicosenylamine, triethylenediamine, hexamethylenetetramine, Ν, Ν, Ν ', Ν'-tetramethylethylenediamine , Ν, Ν, Ν ', Ν'-tetramethylpropyl α-diamine, N, N, N ', N'-tetraethyl-1,3-propanediamine, methyldicyclohexylamine, 2,6-dimethylpyridine, dimethylcyclohexylamine, amidopropyldimethylamine substituted with C10-C22 alkyl or alkenyl, alkyl or alkenyl substituted imidopropyldimethylamine succinic C 10 -C 22, and the like.
    If the amine contains only primary or secondary amino groups, it is necessary to alkylate at least one of the primary or secondary amino groups to a tertiary amine group before quaternizing the amine. In one embodiment, the alkylation of primary amines and secondary amines or mixtures with tertiary amines may be fully or partially alkylated to a tertiary amine and further alkylated to a quaternary salt, all in a single step. If a one-step reaction is used, it may be necessary to properly account for the hydrogens on the nitrogens and provide a base or acid as needed (for example, alkylation to tertiary amine requires removal (neutralization) of the hydrogen (proton) from the product of the alkylation). If alkylating agents, such as alkyl halides or dialkyl sulfates, are used, the product of the alkylation of a primary or secondary amine is a protonated salt and requires a base source to release the amine and to evolve towards the quaternary salt. Such alkylating agents require the alkylation of the tertiary amine, and the product is a quaternary ammonium halide or monomethyl sulfate. On the contrary, epoxides as alkylating agents perform both alkylation and neutralization, such that the intermediate alkylation product is already the free amine. To evolve to the quaternary salt with epoxides, it is necessary to provide the equivalent of an acid to provide a proton for the hydroxy group and a counter anion for the salt.
    Quaternizing Agent [0019] The quaternizing agent suitable for converting the tertiary amine to a quaternary nitrogen compound may be selected from the group consisting of carboxylates, carbonates, cyclic carbonates, phenates, epoxides, carbamates, halides, sulfates. sulfites, sulfides, sulfonates, phosphates, hydrocarbyl-substituted phosphonates, or mixtures thereof. The hydrocarbyl-substituted phenates from which the anion of the quaternary ammonium compound can be derived are of different types. For example, hydrocarbyl-substituted phenates may be derived from phenols of the formula:
    wherein n = 1, 2, 3, 4 or 5, wherein R20 may be hydrogen, or substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl. The hydrocarbon group (s) may be bound to the benzene ring by a keto or thioketo group. Alternatively, the hydrocarbon group (s) may be bonded via an oxygen atom or a nitrogen atom. Examples of such phenols include: o-cresol; m-cresol; p-cresol; 2,3-dimethylphenol; 2,4-dimethylphenol; 2,3,4-trimethylphenol; 3-ethyl-2,4-dimethylphenol; 2,3,4,5-tetramethylphenol, 4-ethyl-2,3,5,6-tetramethylphenol; 2-ethylphenol; 3-ethylphenol; 4-ethylphenyl; 2-n-propylphenol; 2-isopropylphenol; 4-isopropylphenol; 4-n-butylphenol; 4-isobutylphenol; 4-secbutylphénol; 4-t-butylphenol; 4-nonylphenol; 2-dodecylphenol; 4-dodecylphenol; 4-octadecylphenol; 2-cyclohexylphenol; 4-cyclohexylphenol; 2-allylphenol; 4-allylphenol; 2-hydroxydiphenyl; 4-hydroxydiphénol; 4-methyl-4-hydroxybiphenyl; o-methoxyphenol; p-methoxyphenol; p-phenoxyphenol; and 4-hydroxyphenyl-dimethylamine.
    [0020] Also included are phenols of the formula:
    and or
    wherein R20 and R21, which may be the same or different, are as defined above for R20, and m and n are integers, and for each m or n greater than 1, each R20 and R21 may be the same or different.
    Examples of such phenols include: 2,2-dihydroxy-5,5-dimethyldiphenylmethane; 5,5-dihydroxy-2,2-dimethyldiphenylmethane; 4,4-dihydroxy-2,2-diméthyldiméthyldiphénylméthane; 2,2-dihydroxy-5,5-dinonyl-diphenylmethane; 2,2-dihydroxy-5,5-didodécylphénylméthane; 2,2,4,4-tetra-t-butyl-3,3-dihydroxy-5,5-didodécylphénylméthane; and 2,2,4,4-tetra-t-butyl-3,3-dihydroxydiphenylmethane.
    The hydrocarbyl (or alkyl) hydrocarbyl substituted carbonate groups may contain 1 to 50, 1 to 20, 1 to 10 or 1 to 5 carbon atoms per group. In one embodiment, the hydrocarbyl substituted carbonates contain two hydrocarbyl groups which may be the same or different. Examples of suitable hydrocarbyl substituted carbonates include dimethyl, diethyl, ethylene and propylene carbonates and mixtures thereof.
    In another embodiment, the quaternization agent may be a hydrocarbyl epoxide, represented for example by the following formula, in combination with an acid:
    wherein R5, R6, R7 and R8 may be independently hydrogen or a C1-C16 hydrocarbyl group. Examples of hydrocarbyl epoxides may include, but are not limited to, styrene oxide, ethylene oxide, propylene oxide, butylene oxide, epoxyhexane, octylene oxide, and the like. II-ene, stilbene oxide and C2-50 epoxide [0024] The quaternary ammonium salts can be produced in one or two stages. Alkylation of a tertiary amine with an alkyl epoxide can be carried out in a single-step reaction in the presence of an acid as described in US Patent Nos. 4,814,108 and 4,675,180, or in a process in two stages which comprises the alkylation of the tertiary amine in a polar medium and then mixing the alkylated product with an acid. For example, 1 mole of the amine can be treated with X moles of the olefin oxide (where X is the number of tertiary nitrogens in the amine molecule) in the presence of excess water overhead. beyond the amount required by the stoichiometry of the reaction.
    As another example, the pyridine (1 mole) can be treated with an olefin oxide (1 mole) in water (> 1 mole). Triethylenediamine (1 mole) can be treated with an olefin oxide (2 moles) in water (> 2 moles). Hexamine (1 mole) can be treated with an olefin oxide (4 moles) in water (> 4 moles).
    However, the olefin oxide can be used in excess, if required or desired, the excess olefin oxide then reacts with the quaternary ammonium hydroxide. As indicated above, any amount of water may be used as long as it is an excess over the amount required by the stoichiometry of the reaction.
    The reaction can be carried out by contacting and mixing the amine with the olefin oxide in the reaction vessel, wherein water is added to the reaction mixture. The rate of addition of water does not affect the quality of the final product, but slow addition of water can be used to control an exothermic reaction.
    Alternatively, the amine may be mixed with water in the reaction vessel and the olefin oxide is then added to the stirred reaction mixture. The olefin oxide may be added as a pure gas or diluted with an inert carrier (eg, nitrogen); a liquid, a solution in the water; or a solution in a water-miscible organic solvent (e.g. methyl or ethyl alcohol). The rate of addition of the olefin oxide is not critical to the quality of the final product, but a low rate of addition can be used to control an exothermic reaction.
    In another variant of the reaction sequence, the olefin oxide may be mixed with the water in the reaction vessel and the amine is added to the reaction mixture. The amine can be added as pure gas, liquid or solid; a solution in water; of a solution in a water-soluble organic solvent. As with the addition of olefin oxide and water, the rate of addition of the amine can be used to control an exothermic reaction.
    To facilitate the reaction, the mixed reagents can be heated together at a given temperature while the third reagent is added at a rate sufficient to maintain a constant reaction rate and a controllable reaction temperature. Alternatively, the reactants may be heated in a pressure vessel, but when the reactants are heated to promote the reaction, it is preferable to avoid a temperature above 100 ° C to prevent decomposition of the hydroxide. quaternary ammonium. The second step of the reaction sequence comprises neutralizing the quaternary ammonium hydroxide formed in the first step with the organic acid.
    In general, sufficient acid is mixed with the solution obtained in the first step to neutralize the quaternary ammonium hydroxide. However, an excess of acid may be used if necessary, for example when only one carboxylic acid group of a polybasic acid is to be neutralized. The neutralization reaction can be carried out in the absence of any solvent; in the presence of an alcohol, for example methanol, ethanol, isopropanol, 2-ethoxyethanol, 2-ethylhexanol, or ethylene glycol; in the presence of any other polar organic solvent, for example acetone, methyl ethyl ketone, chloroform, carbon tetrachloride, or tetrachloroethane; in the presence of a hydrocarbon solvent, for example hexane, heptane, white spirit, benzene, toluene or xylene; or in the presence of a mixture of any of the above solvents.
    The organic acid which can be used in the second step of the reaction and which forms the anion in the quaternary ammonium salt can be, for example, a carboxylic acid, a phenol, a sulphurized phenol, or the like. sulfonic acid.
    The neutralization reaction can be carried out at room temperature, but generally a high temperature is used. When the reaction is complete, water and any solvents used can be removed by heating the reaction product under vacuum. The product is usually diluted with mineral oil, diesel fuel, kerosene, or an inert hydrocarbon solvent to prevent the product from being too viscous.
    In another embodiment, the quaternization agent may be a hydrocarbyl substituted carboxylate, also known as an ester of a carboxylic acid. The corresponding carboxylate acids may be selected from mono-, di- or polycarboxylic acids. The monocarboxylic acids may include an acid of the formula R-COOH, wherein R is hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, or aryl group containing from 1 to 50 carbon atoms. Examples of such acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, palmitic acid, stearic acid, cyclohexanecarboxylic acid, acid 2, and the like. methylcyclohexane carboxylic acid, 4-methylcyclohexanecarboxylic acid, oleic acid, linoleic acid, cyclohex-2-enoic acid, benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, salicylic acid, 2-hydroxy-4-methylbenzoic acid, 2-hydroxy-4-ethylsalicylic acid, p-hydroxybenzoic acid, 3,5-di- tert-butyl-4-hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, o-methoxybenzoic acid and p-methoxybenzoic acid.
    The dicarboxylic acids may comprise an acid of the formula:
    wherein n is zero or an integer, including, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and suberic acid. Also included are acids of the formula:
    where x is zero or an integer, y is zero or an integer and x and y may be the same or different and R is hydrogen, or alkyl, cycloalkyl, alkenyl, cycloalkenyl, or aryl, substituted or unsubstituted containing from 1 to 50 carbon atoms as described above. Examples of such acids include alkyl or alkenyl succinic acids, 2-methylbutanedioic acid, 2-ethylpentanedioic acid, 2-n-dodecylbutanedioic acid, 2-n-dodecenylbutanedioic acid , 2-phenylbutanedioic acid, and 2- (p-methylphenyl) butanedioic acid. Also included are polysubstituted alkyl dicarboxylic acids in which other R groups as described above may be substituted on the alkyl chain. Examples include 2,2-dimethylbutanedioic acid, 2,3-dimethylbutanedioic acid; 2,3,4-trimethylpentanedioic acid, 2,2,3-trimethylpentanedioic acid, and 2-ethyl-3-methylbutanedioic acid.
    The dicarboxylic acids also comprise acids of the formula
    wherein r is an integer of 2 or more. Examples include maleic acid, fumaric acid, pent-2-enedioic acid, hex-2-enedioic acid; hex-3-enedioic acid; 5-methylhex-2-enedioic acid; 2,3-dimethylpent-2-enedioic acid; 2-methylbut-2-enedioic acid; 2-dodecylbut-2-enedioic acid; and 2-polyisobutylbut-2-enedioic acid.
    The dicarboxylic acids also include aromatic dicarboxylic acids, for example phthalic acid, isophthalic acid, terephthalic acid, and substituted phthalic acids of the formula:
    wherein R is defined as above and n = 1, 2, 3 or 4, and when n> 1, then the R groups may be the same or different. Examples of such acids include 3-methylbenzene-1,2-dicarboxylic acid; 4-phenylbenzene-1,3-dicarboxylic acid; 2- (1-propenyl) benzene-1,4-dicarboxylic acid; and 3,4-dimethylbenzene-1,2-dicarboxylic acid.
    For alkylation with an alkyl carboxylate, it is desirable that the corresponding carboxylate acid has a pKa of less than 4.2. For example, the corresponding acid of the carboxylate may have a pKa of less than 3.8, such as less than 3.5, a pKa of less than 3.1 being particularly desirable. Examples of suitable carboxylates may include, but are not limited to, maleate, citrate, fumarate, phthalate, 1,2,4-benzenetricarboxylate, 1,2,4,5-benzenetetracarboxylate, nitrobenzoate, nicotinate, oxalate, aminoacetate, and salicylate.
    In another embodiment, the quaternary ammonium salt may be prepared by ion exchange reactions, such as
    wherein X is a halide, R is defined as above and Ar is an aromatic group. The quaternary salt can also be prepared by direct alkylation of a tertiary amine or polyamine. Alkylating agents include, but are not limited to, an alkyl halide, an alkyl carbonate, an alkyl sulfate, a cyclic carbonate, an alkyl epoxide, an alkyl carboxylate, and a carbamate. alkyl.
    In certain aspects of the present application, the quaternary ammonium salt compositions of the present invention may be used in combination with a fuel-soluble carrier. Such supports can be of different types, such as liquids or solids, for example waxes. Examples of liquid carriers include, but are not limited to, mineral oil and oxygenates, such as liquid polyalkoxylated ethers (also known as polyalkylene glycols or polyalkylene ethers), liquid polyalkoxylated phenols, liquid polyalkoxylated esters, amines liquid polyalkoxylates, and mixtures thereof. Examples of oxygenate supports can be found in US Patent No. 5,752,989, issued May 19, 1998 to Henly et al., The disclosure of which is hereby incorporated by reference in its entirety. Additional examples of oxygenate supports include alkyl-substituted aryl polyalkoxylates disclosed in US Patent Publication No. 2003/0131527, published July 17, 2003 issued to Colucci et al., The disclosure of which is incorporated herein by reference. complete for reference.
    [0041] In other aspects, quaternary ammonium salt compositions may not contain a carrier. For example, some compositions of the present invention may not contain mineral oil or oxygenates, such as the oxygenates described above.
    One or more additional optional compounds may be present in the fuel composition of the disclosed embodiments. For example, the fuels may contain conventional amounts of cetane promoters, corrosion inhibitors, cold flow improvers (CFPP additives), freezing point depressants, solvents, agents and the like. demulsifiers, lubricating additives, friction modifiers, amine stabilizers, combustion improvers, dispersants, antioxidants, heat stabilizers, conductivity enhancers, metal deactivators, labeling dyes, organic nitrate ignition accelerators, and cyclomatic tricarbonyl manganese compounds, and the like. In some aspects, the compositions described herein may contain about 10% by weight or less, or in other aspects about 5% by weight or less, based on the total weight of the concentrated additive, or one or several of the additives above. Similarly, the fuels may contain appropriate amounts of conventional fuel blend components such as methanol, ethanol, dialkyl ethers and the like.
    In certain aspects of the embodiments disclosed, organic nitrate ignition accelerators which include aliphatic or cycloaliphatic nitrates in which the aliphatic or cycloaliphatic group is saturated, and which contain up to about 12 carbon atoms, may to be used. Examples of organic nitrate ignition accelerators that can be used are methyl nitrate, ethyl nitrate, propyl nitrate, isopropyl nitrate, allyl nitrate, butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate, amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, hexyl nitrate , heptyl nitrate, 2-heptyl nitrate, octyl nitrate, isooctyl nitrate, 2-ethylhexyl nitrate, nonyl nitrate, decyl nitrate, undecyl nitrate, dodecyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate, cyclododecyl nitrate, 2-ethoxyethyl nitrate, 2- (2-ethoxyethyl) ethyl nitrate, tetrahydrofuranyl nitrate, and like. Mixtures of these materials can also be used.
    Examples of suitable optional metal deactivators useful in the compositions of the present invention are disclosed in U.S. Patent No. 4,482,357, issued November 13, 1984, the contents of which are incorporated herein in its entirety. for reference. Such metal deactivators include, for example, salicylidene-o-aminophenol, disalicylidene ethylenediamine, disalicylidene propylenediamine, and N, N'-disalicylidene-1,2-diaminopropane.
    Optional cyclomatic tricarbonyl manganese compounds that can be employed in the compositions of the present application include, for example, manganese cyclopentadienyl tricarbonyl, manganese methyl-cyclopentadienyl tricarbonyl, manganese indenyl tricarbonyl, and the like. ethylocyclopentadienyl tricarbonyl manganese. Still other examples of cyclomatic tribarbonyl manganese compounds are disclosed in U.S. Patent No. 5,575,823, issued November 19, 1996, and U.S. Patent No. 3,015,668, issued January 2, 1962. both of which are incorporated herein in their entirety for reference.
    In formulating the fuel compositions of the present application, the additives may be employed in amounts sufficient to reduce or inhibit the formation of deposits in a fuel system or in a combustion chamber of an engine and / or or a crankcase. In some aspects, the fuels may contain minor amounts of the reaction product described above, which controls or reduces the formation of deposits in the engine, for example deposits on the injectors in diesel engines. For example, the diesel fuels of the present invention may contain, based on active ingredients, an amount of the quaternary ammonium salt in the range of about 5 mg to about 200 mg of reaction product per kg of fuel, as in the range of about 10 mg to about 150 mg per kg of fuel or in the range of about 30 mg to about 100 mg of the quaternary ammonium salt per kg of fuel. In aspects where a carrier is employed, the fuel compositions may contain, based on active ingredients, a carrier amount in the range of about 1 mg to about 100 mg carrier per kg of fuel, such as about 5 mg to about 50 mg of carrier per kg of fuel.
    The active ingredient base excludes the weight (i) of the unreacted components associated with and remaining in the product as it is produced and used, and (ii) solvents, if any, used in the manufacture of the product either during or after its formation but before the addition of a support, if a support is used.
    The additives of the present invention, including the reaction product described above, and optional additives used in the formulation of the fuels of the present invention, may be blended into the base diesel fuel individually or in various forms. -searches. In some embodiments, the additive components of the present application can be blended into the diesel fuel by simultaneously using a concentrated additive, since this takes advantage of the mutual compatibility and convenience provided by the combination of ingredients when they are in the form of a concentrated additive. Similarly, the use of a concentrate can reduce the mixing time and reduce the possibility of mixing errors.
    The fuels of the present application can be used for the operation of a diesel engine. The engine includes stationary engines (eg engines used in power generation facilities, pumping stations, etc.) and mobile engines (eg motors used to produce motion in automobiles, trucks, road equipment, military vehicles, etc.). For example, fuels may include any and all fuels for gasoline and middle distillate, diesel fuels, bio-renewable fuels, biodiesel fuels, liquefied natural gas (LNG) fuels, jet fuel, alcohols, ethers, kerosene, low sulfur fuels, synthetic fuels, such as Fischer-Tropsch fuels, liquefied petroleum gas, bunker fuels, liquefied coal fuels (CTL), liquefied biomass fuels (BTL), high asphaltene fuels , fuels derived from coal (natural, cleaned and petroleum coke), genetic biofuels and crops and extracts thereof, and natural gas. It should be understood that the "bio-renewable fuels" used here mean any fuel that is derived from resources other than oil. Such resources include, but are not limited to, seeds, corn, soybeans and other crops; herbs, such as switchgrass, miscanthus, and hybrid grasses; algae, seaweed, vegetable oils; natural fats; and mixtures thereof. In one aspect, the bio-renewable fuel may comprise monohydroxy alcohols, such as those comprising from 1 to about 5 carbon atoms. Non-limiting examples of monohydroxy alcohols include methanol, ethanol, propanol, n-butanol, isobutanol, 1-butyl alcohol, amyl alcohol, and isoamyl alcohol.
    Therefore, aspects of the present application relate to methods for reducing the amount of deposits on the engine injectors having at least one combustion chamber and one or more direct fuel injectors in fluid connection with the combustion chamber. . In another aspect, the quaternary ammonium salts described herein may be combined with relatively high molecular weight quaternary ammonium salts comprising one or more polyolefin groups; such as quaternary ammonium salts of polymono-olefins, polyhydrocarbyl succinimides; Mannich polyhydrocarbyl compounds; polyhydrocarbyl amides and esters, wherein a "relatively high molecular weight" means a number average molecular weight greater than 600 daltons. The foregoing quaternary ammonium salts disclosed, for example, in U.S. Patent Nos. 3,468,640; 3,778,371; 4,056,531; 4,171,959; 4,253,980; 4,326,973; 4,338,206; 4,787,916; 5,254,138; 7,906,470; 7,947,093; 7,951,211; in US Patent Application Publication No. 2008/0113890; in European Patent Applications No. EP 0293192; EP 2033945; and in PCT Application No. WO 2001/110860.
    In some aspects, the methods include injecting a hydrocarbon-based compression ignition fuel comprising the quaternary ammonium salt of the present invention through the diesel engine injectors into the fuel chamber. combustion, and ignition of the compression ignition fuel. In some aspects, the process may also include mixing in diesel fuel at least one of the additional optional ingredients described above.
    In one embodiment, the diesel fuels of the present application may be substantially free, especially free, of conventional dispersant succinimide compounds. In another embodiment, the fuel is substantially free of a quaternary ammonium salt of a hydrocarbyl succinimide or a quaternary ammonium salt of a Mannich hydrocarbyl compound having a number average molecular weight greater than 600 daltons. . The term "essentially free" is defined for the purposes of this application as being concentrations that have substantially no measurable effect on injector cleanliness or deposit formation.
    EXAMPLES
    The following examples illustrate the exemplary embodiments of the present disclosure. In these examples and elsewhere in this application, all parts and percentages are by weight unless otherwise indicated. These examples are intended to be presented by way of illustration only, but not to limit the scope of the invention described herein.
    Comparative Example 1 - Conventional Polyisobutylene Succinimide (PIBSI) An additive was produced by the reaction of a polyisobutylene succinic anhydride with a number average molecular weight of 950 (PIBSA) with tetraethylenepentamine (ΤΕΡΑ) in a molar ratio of PIBSA / TEPA = 1/1. A modified procedure of US Patent 5,752,989 has been used. PIBSA (551 g) was diluted in 200 grams of aromatic solvent 150 under a nitrogen atmosphere. The mixture was heated to 115 ° C. The ΤΕΡΑ was then added by an addition funnel. The addition funnel was rinsed with an additional 50 grams of aromatic solvent 150. The mixture was heated at 180 ° C for about 2 hours under a gentle nitrogen sweep. The water was harvested in a Dean-Stark trap. The product obtained was a brownish oil.
    Comparative Example 2: PIBSA-DMAPA-E6 [0054] PIBSI was prepared as in Comparative Example 1 except that dimethylaminopropylamine (DMAPA) was used instead of ΤΕΡΑ. The PIBSI obtained (PD, about 210 g) was reacted with 36.9 grams of 1,2-epoxyhexane (E6), 18.5 grams of acetic acid (18.5 g) and 82 grams of 2-ethylhexanol until the reaction was complete. at 90 ° C for 3 hours. The volatile components were removed under reduced pressure to give the desired quaternary salt (quat).
    Comparative Example 3: Dimethyl PIBSA-DMAPA-oxalate [0055] PIBSI of Comparative Example 2 (146 g) was reacted with 13.3 grams of dimethyl oxalate in 50 grams of aromatic solvent 150 to 150 ° C. about 2 hours. The product obtained was a brownish oil.
    Example of the invention 1 - (C8) 3NMe [0056] Trioctylmethylammonium chloride (70 grams) was mixed with 130 grams of heptane. The mixture was extracted five times with 70 grams of sodium acetate (about 16% by weight in water). Volatile components from the organic layer obtained were removed under reduced pressure to give a quat acetate. An FTIR spectrum showed significant peaks at 1578 and 1389 cm -1, characteristic of a carboxylate salt.
    Example of the Invention 2: (C12) 2NMe2 [0057] A commercial quaternary ammonium product (C12) 2NMe2 + NO2- was distilled under vacuum to remove the volatile components to give the desired product.
    Example of the Invention 3 - Dimethyloctadecyl (2-hydroxyhexyl) ammonium acetate [0058] A mixture of C18-N-Me2 (118 g), 39 grams of 1,2-epoxyhexane, 26 grams of acetic acid, and 76 grams of 2-ethylhexanol was slowly heated to 90 ° C under an inert atmosphere. The mixture was heated at 90 ° C for 1.5 hours. The volatile components were then removed under reduced pressure to give the desired product.
    In the following example, an injector deposition test was performed on a diesel engine using a standard diesel engine fuel injector test, CEC F-98-08 (DW10) which is described. below.
    Diesel Engine Test Protocol [0060] A DW10 test, which had been developed by the European Co-ordination Council (ECC), was used to demonstrate the propensity of fuels to cause fouling of fuel injectors and was also used. to demonstrate the ability of certain fuel additives to prevent or control these deposits. Additional assessments used CEC protocol F-98-08 for coking tests of common rail diesel engines and direct injection. An engine dynamometer test bench was used for the installation of the Peugeot DW10 diesel engine to perform injector coking tests. The engine was a 2.0-liter four-cylinder engine. Each combustion chamber had four valves and the injectors were DI piezo injectors with a Euro V classification.
    The central procedure of the protocol was to run the engine for a cycle of 8 hours and let the engine cool (engine off) for a prescribed time. The previous sequence was repeated four times. At the end of each hour, the engine power was measured while the engine was running at rated conditions. The propensity of the fuel to foul the injectors was characterized by a difference in the nominal power observed between the beginning and the end of each test cycle.
    The preparation of the test included rinsing the previous test fuel from the engine before removing the injectors. The test injectors were inspected, cleaned, and reinstalled on the engine. If new injectors were selected, the new injectors were subjected to a 16-hour break-in cycle. Then the engine was started using the desired test cycle program. Once the engine was warm, power was measured at 4,000 rpm and at full load to verify full power restoration after injector cleaning. If the power measurements were within the specification, the test cycle was started. Table 1 below gives a representation of the DW10 coking cycle that was used to evaluate the fuel additives according to the invention.
    Table 1 - Representation of the DW10 coking cycle for one hour.
    [0063] Various fuel additives were tested using the previous engine test procedure in a very low sulfur diesel fuel containing zinc neodecanoate, 2-ethylhexyl nitrate, and an ester type friction modifier. fatty acid (basic fuel). A "fouling" phase consisting solely of the basic fuel without additive was started, followed by a "cleaning" phase consisting of the base fuel with additive. All measurements were made with an 8-hour fouling phase and an 8-hour cleaning phase, unless otherwise specified. The percentage power recovery was calculated using the power measurement at the end of the "fouling" phase and the power measurement at the end of the "cleaning" phase. The percentage power recovery was determined by the following formula Percentage power recovery = (DU-CU) / DU x 100 where DU represents the percent power loss at the end of a fouling phase without the additive, CU represents the percent power at the end of a cleaning phase with the fuel additive, and the power is measured according to the DW10 test, CEC protocol F98-08.
    Table 2
    Thermogravimetric analysis (TGA) was performed according to ISO-4154. Specifically, the test was run from 50 ° to 900 ° C with a rate of temperature increase of 20 ° C per minute under a nitrogen atmosphere with a flow rate of 60 ml per minute. For the purpose of comparison, the percentage of flow remaining for the compositions tested was also determined in the XUD9 test engine, as shown in Table 3. The XUD9 test method is intended to evaluate the ability of a fuel to check the formation of deposits on the injector nozzles of a diesel engine with indirect injection. XUD9 test results are expressed as percentages of airflow loss at various injector needle lift points. The air flow measurements were performed with an ISO 4010 compliant airflow mount.
    Before carrying out the test, the nozzles of the injectors were cleaned and checked for their air flow for a lift of 0.05, 0.1, 0.2, 0.3 and 0.4 mm. . The nozzles are removed if the airflow is outside the range from 250 ml / min to 320 ml / min for 0.1 mm lift. The nozzles are assembled in the injector bodies and the opening pressures are set at 115 ± 5 bar. A slave set of injectors is also mounted on the engine. The previous test fuel is drained out of the system. The engine is run for 25 minutes to completely bleed the fuel system. Meanwhile, all spilled fuel is discarded and not recovered. The motor is then set to test speed and load and all specified parameters are checked and adjusted to the test specification. The slave injectors are then replaced by the test units. Air flow is measured before and after the test. An average of 4 injector flow rates at 0.1 mm of lift are used to calculate the percentage of fouling. The degree of flow remaining = 100 - percentage of fouling. The results are shown in the table below.
    Table 3
    As shown in the previous example, tests 4, 5 and 6, the quaternary ammonium salt of the disclosed embodiments was superior to the conventional dispersants and quaternary ammonium salts of Tests 1, 2 and 3 in a direct injection diesel engine at a treatment rate much lower than that of tests 1, 2 and 3 for example. The results are surprising since the same quaternary ammonium salts of tests 4 and 5 exhibit a relatively poor performance in an indirect injection diesel engine according to the XUD9 test. In other words, the evaluation of various quaternary ammonium salts in an indirect injection diesel engine would not have led to the selection of the disclosed quaternary ammonium salts to improve efficiency in a direct injection diesel engine. In addition, it is believed that the disclosed quaternary ammonium salts described herein may be effective in keeping injector surfaces clean for engines and may be used to clean fouled fuel injectors.
    It should be noted that, as used in this specification and the related claims, the singular forms "a", "a", "the" and "the" include plural referents, unless otherwise expressly unequivocally to a single referent. Thus, for example, the reference to "an antioxidant" includes two or more different antioxidants. As used herein, the term "understand" and its grammatical variants are intended to be nonlimiting, so that the enumeration of the elements of a list is not done by excluding other similar elements that may be substituted or add to the items listed.
    For the purposes of this specification and related claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, shall be understood to be modified in any case by the term "about". Therefore, unless otherwise indicated, the numerical parameters indicated in the following specification and related claims are approximations which may vary depending on the desired properties sought by the present invention. Finally, and without seeking to limit the application of the doctrine of equivalents to the scope of the claims, each numeric parameter must at least be interpreted in light of the number of significant digits indicated and by applying ordinary rounding techniques.
    Although particular embodiments have been described, alternatives, modifications, variations, improvements and substantial equivalents that are or may be at present unforeseen may be imposed on applicants and other skilled persons. Accordingly, the related claims as filed and as amended may be intended to encompass all of these alternatives, modifications, variations, improvements and substantial equivalents.
    权利要求:
    Claims (22)
    [1]
    A fuel composition for a direct injection diesel engine comprising: a major amount of fuel and an effective minor amount of a quaternary ammonium salt having a thermogravimetric (TGA) weight loss of greater than 50% by weight at 350 ° C; wherein the amount of quaternary ammonium salt present in the fuel is sufficient to improve the performance of a direct fuel injection diesel engine having consumed the composition as compared to the performance of such engine having consumed a fuel composition which does not contain the quaternary ammonium salt.
    [2]
    The fuel composition of claim 1, wherein the fuel has a sulfur content of 50 ppm by weight or less.
    [3]
    The fuel composition according to claim 1 or 2, wherein the quaternary ammonium salt comprises a compound of the formula

    wherein each of R1, R2, R3 and R4 is selected from hydrocarbyl groups containing from 1 to 50 carbon atoms, wherein at least one and not more than three of R1, R2, R3 and R4 is a hydrocarbyl group containing 1 to 4 carbon atoms and at least one of R1, R2, R3 and R4 is a hydrocarbyl group containing from 8 to 50 carbon atoms, M "is selected from the group consisting of carboxylates, halides, sulfates, nitrates, nitrides nitrites, hyponitrites, phenates, carbamates, carbonates, and mixtures thereof, wherein the carboxylate is not an oxalate.
    [4]
    The fuel composition according to claim 3, wherein each hydrocarbyl group is independently linear, branched, substituted, cyclic, saturated, unsaturated, or contains one or more hetero atoms.
    [5]
    The fuel composition according to claim 3 or 4, wherein R1, R2, R3 and R4 are each selected from hydrocarbyl groups containing from 1 to 20 carbon atoms, provided that at least one of R1, R2, R3 and R4 contains from 8 to 20 carbon atoms.
    [6]
    The fuel composition of claim 5, wherein the hydrocarbyl groups are selected from alkyl, alkenyl, and alkanol groups.
    [7]
    The fuel composition according to any one of the preceding claims, wherein the amount of quaternary ammonium salt in the fuel is in the range of about 5 to about 200 ppm by weight based on the total weight of the fuel.
    [8]
    The fuel composition according to any one of the preceding claims, wherein the amount of quaternary ammonium salt in the fuel is in the range of about 10 to about 150 ppm by weight based on the total weight of the fuel.
    [9]
    The fuel composition according to any one of the preceding claims, wherein the amount of quaternary ammonium salt in the fuel is in the range of about 30 to about 100 ppm by weight based on the total weight of the fuel.
    [10]
    The fuel composition according to any one of the preceding claims, wherein said improved engine behavior comprises restoring the engine power by at least about 80% when measured according to CEC test F98-08. DW10.
    [11]
    The fuel composition according to any one of the preceding claims, wherein said improved engine behavior comprises restoring the engine power by at least about 90% when measured according to CEC test F98-08. DW10.
    [12]
    The fuel composition according to any one of the preceding claims, wherein said improved engine behavior comprises restoring the engine power by at least about 100% when measured according to CEC test F98-08. DW10.
    [13]
    A method for improving the behavior of an injector of a direct injection diesel engine comprising the operation of the engine with a fuel composition containing a major amount of fuel and from about 5 to about 200 ppm by weight, on the basis of the total weight of fuel, of a quaternary ammonium salt having a thermogravimetric (TGA) weight loss of greater than 50% by weight at 350 ° C, wherein the quaternary ammonium salt present in the fuel improves the efficiency of the engine injector by at least about 80% when measured according to a CEC F98-08 DW10 test.
    [14]
    The method of claim 13, wherein the engine comprises a direct injection diesel engine.
    [15]
    The process according to claim 13 or 14, wherein the quaternary ammonium salt comprises a compound of the formula

    wherein each of R1, R2, R3 and R4 is selected from hydrocarbyl groups containing from 1 to 50 carbon atoms, wherein at least one and not more than three of R1, R2, R3 and R4 is a hydrocarbyl group containing 1 to 4 carbon atoms and at least one of R1, R2, R3 and R4 is a hydrocarbyl group containing from 8 to 50 carbon atoms, M 'is selected from the group consisting of carboxylates, nitrates, halides, sulfates, nitrides nitrites, hyponitrites, phenates, carbamates, carbonates, and mixtures thereof.
    [16]
    The process of claim 15, wherein each hydrocarbyl group is independently linear, branched, substituted, cyclic, saturated, unsaturated, or contains one or more hetero atoms.
    [17]
    17. A method of driving a direct injection diesel engine comprising burning in the engine a fuel composition containing a major amount of fuel and from about 5 to about 200 ppm by weight, based on the weight total fuel, a quaternary ammonium salt having a weight loss by thermogravimetric analysis (TGA) greater than 50% by weight at 350 ° C.
    [18]
    The process of claim 17, wherein the quaternary ammonium salt comprises a compound of the formula

    wherein each of R1, R2, R3 and R4 is selected from hydrocarbyl groups containing from 1 to 50 carbon atoms, wherein at least one and not more than three of R1, R2, R3 and R4 is a hydrocarbyl group containing 1 to 4 carbon atoms and at least one of R1, R2, R3 and R4 is a hydrocarbyl group containing from 8 to 50 carbon atoms, M "is selected from the group consisting of carboxylates, nitrates, halides, sulfates, nitrides nitrites, hyponitrites, phenates, carbamates, carbonates, and mixtures thereof.
    [19]
    The process of claim 18, wherein each hydrocarbyl group is independently, linear, branched, substituted, cyclic, saturated, unsaturated, or contains one or more heteroatoms.
    [20]
    20. A concentrated additive for a fuel for use in a direct injection diesel engine comprising a quaternary ammonium salt having a thermogravimetric (ATG) weight loss of greater than 50% by weight at 350 ° C and at least one component selected from the group consisting of diluents, carrier fluids, compatibilizers, cetane promoters, corrosion inhibitors, cold flow improvers (CFPP additives), depressants freezing point, solvents, demulsifying agents, lubricating additives, friction modifiers, amine stabilizers, combustion improvers, dispersing agents, antioxidants, hot stabilizers, conductivity enhancers, metal deactivators, marking dyes, organic nitrate ignition accelerators, and tricarbonyl manganese compounds cyclomatic.
    [21]
    The concentrated additive of claim 20, wherein the quaternary ammonium salt comprises a compound of the formula

    wherein each of R1, R2, R3 and R4 is selected from hydrocarbyl groups containing from 1 to 50 carbon atoms, wherein at least one and not more than three of R1, R2, R3 and R4 is a hydrocarbyl group containing 1 to 4 carbon atoms and at least one of R1, R2, R3 and R4 is a hydrocarbyl group containing from 8 to 50 carbon atoms, M 'is selected from the group consisting of carboxylates, nitrates, nitrides, halides, sulfates nitrites, hyponitrites, phenates, carbamates, carbonates, and mixtures thereof, wherein the carboxylate is not an oxalate.
    [22]
    22. The concentrate additive of claim 21, wherein each hydrocarbyl group is independently linear, branched, substituted, cyclic, saturated, unsaturated, or contains one or more heteroatoms.
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    同族专利:
    公开号 | 公开日
    AU2012227347B2|2014-04-17|
    DE102012020501A1|2013-05-16|
    TWI521055B|2016-02-11|
    GB2496514B|2014-07-09|
    GB201220148D0|2012-12-26|
    KR20130052507A|2013-05-22|
    TW201321495A|2013-06-01|
    US9574149B2|2017-02-21|
    CN103102998B|2015-07-15|
    GB2496514A|2013-05-15|
    MY179415A|2020-11-05|
    KR101475119B1|2014-12-22|
    DE102012020501B4|2016-05-12|
    AU2012227347C1|2015-08-13|
    US20130118062A1|2013-05-16|
    AU2012227347A1|2013-05-30|
    SG190527A1|2013-06-28|
    CN103102998A|2013-05-15|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US13/294,672|US9574149B2|2011-11-11|2011-11-11|Fuel additive for improved performance of direct fuel injected engines|
    US13/294672|2011-11-11|
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